WO2014014228A1

WO2014014228A1 - Fuel supplying apparatus and system for direct carbon fuel cell

Info

Publication number: WO2014014228A1
Application number: PCT/KR2013/006097
Authority: WO
Inventors: 황준영; 강희석; 강경태; 이상호
Original assignee: 한국생산기술연구원
Priority date: 2012-07-16
Filing date: 2013-07-09
Publication date: 2014-01-23
Also published as: CN104471770B; CN104471770A; KR101341512B1; US20150188166A1; US9837675B2

Abstract

Disclosed is a fuel supplying apparatus, for a direct carbon fuel cell, which has improved output density by ensuring the flow properties of an anode medium. The fuel supplying apparatus for a direct carbon fuel cell comprises: a flow pipe which forms a cylindrical flow path in the vertical direction around a tube-shaped cell contained in an anode medium in which a carbon fuel is mixed; and a bubbling means which provides a gas from below the flow pipe to the inside of the anode medium and thus enables the anode medium to flow by the vertical flow of the gas. Consequently, the anode medium is provided to the anode of the tube-shaped cell by the flow.

Description

Fuel supply system and system of direct carbon fuel cell

The present invention relates to a direct carbon fuel cell, and more particularly, to a fuel supply device and system for a direct carbon fuel cell having improved output density by securing fluidity of an anode medium.

While traditional developed countries are working to reduce carbon emissions, the energy needs of emerging economies such as China and India are expected to surpass OECD countries. On the other hand, coal is buried globally in a large amount and is expected to become an important energy source in the global energy market such as the US and China.

Globally, carbon dioxide emissions are continuously increasing, and the development of an efficient carbon conversion method is needed. Recently, technologies for obtaining clean coal from which carbon dioxide is separated and a technical approach using coal as a direct fuel have been attempted. CO2 separation technology is generally difficult to apply universally due to different regional soils depending on the burial area, and the technical approach is difficult because of efficiency and cost problems.

However, the direct carbon fuel cell (DCFC) is a coal system, which has the advantage of utilizing gigawatt-scale large-scale power generation and waste heat, and has emerged as a very important technology in the concept of distributed generation.

The direct carbon fuel cell does not use hydrogen gas as a fuel gas, but uses a fuel and carbon dioxide with economical and large reserves as a direct fuel, and as a reducing gas, a new concept fuel cell operated using air like other fuel cells. to be.

Power generation systems using direct carbon fuel cells have higher energy conversion efficiencies than conventional thermal power plants, and in theory have a high efficiency of over 80%, which is the highest level in the existing fuel cells. In addition, since there are abundant reserves in the world and economical coal is used as fuel, various coal sources for power generation are available, and it is possible to fundamentally reduce the emission of environmental pollutants such as SOx, NOx and PM generated during combustion. In addition to the advantages, there is no noise, pollution-free, because the power is produced by the chemical reaction using carbon directly, it can reduce the emission of CO ₂ more than 90% compared to the existing thermal power plant.

In the direct carbon fuel cell, oxygen ions generated by the reduction reaction of oxygen in the cathode move to the anode through the electrolyte, and in the anode, carbon dioxide is generated by the reaction of oxygen ions and carbon, and the carbon dioxide is oxygen again. It reacts with ions to produce carbonate ions, and the generated carbonate ions oxidize carbon to generate carbon dioxide and electrons.

A schematic diagram of the power generation of the direct carbon fuel cell is shown in FIG. 1.

In the cathode support type solid oxide electrolyte direct carbon fuel cell using molten carbonate as an anode medium, first, a carbon fuel and an anode medium should be mixed well to improve the power density by reducing the concentration polarization of the anode. There is a need to force the battery.

To this end, a method of forcibly flowing molten carbonate, which is an anode medium, is required.

In order to forcibly flow the molten carbonate, which is the anode medium, a method using a liquid pump has been conventionally proposed.

However, liquid pumps have difficulty in flowing molten carbonate efficiently and practically due to the nature of the molten carbonate having high temperature (700 ° C to 1000 ° C) and high corrosion resistance.

An object of the present invention is to provide a fuel supply apparatus and system for a direct carbon fuel cell which improves the power density by forcibly flowing molten carbonate, which is an anode medium, to reduce concentration polarization of the anode.

Another object of the present invention is to provide a fuel supply apparatus and system for a direct carbon fuel cell capable of supplying a fuel cell while forcibly mixing a fuel medium consisting of carbon fuel and molten carbonate.

It is another object of the present invention to form a flow path tube around at least one tubular cell including a cathode support and a solid oxide electrolyte, and to provide fluidity of the anode medium in the flow path by carbon dioxide flow. A fuel supply device and system are provided.

Another object of the present invention is to form a flow pipe around the tubular cell to ensure the fluidity of the anode medium to form a separation pipe in the flow path pipe to vertically flow the anode medium on the outer flow path between the flow pipe and the separation pipe inside the separation pipe To provide a fuel supply apparatus and system for a direct carbon fuel cell for flowing the anode medium on the inner passage of the.

Still another object of the present invention is to provide a fuel supply device and system for a direct carbon fuel cell which forms a flow pipe around a tubular cell and forms a separation pipe inside the flow pipe to prevent gas from flowing into the outside from the separation pipe. In providing.

A fuel supply apparatus for a direct carbon fuel cell according to the present invention includes: a separation tube having a cylindrical inner flow path formed in a vertical direction around a tubular cell contained in a fuel medium mixed with carbon fuel and having a through hole through which the fuel medium can enter and exit; A flow path tube forming a cylindrical outer flow path in a vertical direction around the separation pipe; And bubbling means for supplying gas to the outer flow path between the flow path pipe and the separation pipe, wherein the anode medium on the outer flow path primarily flows as the gas supplied to the outer flow path moves vertically. And the anode medium on the inner flow path connected to the outer flow path and the through hole is secondarily flown.

Here, the flow path tube is formed by the collecting portion of the lower shape is wide, the gas supplied to the lower can be guided to the outer flow path by the collecting portion.

And, the bubbling means includes a supply pipe for supplying the gas and the end of the supply pipe may be configured to supply the gas to the outer flow path between the flow path pipe and the separation pipe.

In addition, the supply pipe of the bubbling means may be configured to extend from the top to the bottom along the outer wall of the flow pipe.

The supply pipe may be formed spirally along the outer wall of the flow path pipe.

The dispersing member may further include a dispersing member configured to disperse the gas supplied from the bubbling means and to supply the upper portion to the outer flow passage between the flow passage tube and the separation tube.

The dispersion member may be configured as a ring-shaped plate having a plurality of through holes.

In addition, the dispersion member may include a porous layer.

And the bubbling means independently generates and provides the gas.

The bubbling means may recycle and supply the gas generated by the electrochemical reaction of the carbon fuel and then discharged to the outside of the anode medium.

In addition, the through hole of the separation pipe may be formed to have an incline rising outward.

In addition, the separation pipe may be formed in contact with the through hole is a guide for guiding the flow of the fluid to the outside on the inner wall.

In addition, the separation tube may form the inner flow path around a plurality of tubular cells.

On the other hand, the direct carbon fuel cell system according to the present invention, at least one tubular cell having a structure in which the cathode is formed inside, the anode is formed on the outer surface and the electrolyte is formed of a solid oxide between the cathode and the anode; And the fuel supply device for supplying an anode medium forcedly flowing to the tubular cell.

Therefore, according to the present invention, the anode medium can be forcibly supplied to the direct carbon fuel cell while the fluidity of the anode medium in the flow path is ensured and the carbon fuel and the anode medium are mixed.

In addition, according to the present invention, a separation pipe is formed in the flow path pipe, and the flow of the fuel medium in the inner flow path in the separation pipe may occur due to the flow of the anode medium on the external flow path between the flow path pipe and the separation pipe.

Thereby, the output density is improved by reducing the concentration polarization of the anode of the tubular cell of the direct carbon fuel cell.

In addition, according to the action of the separation tube it can be prevented that the gas of the external flow path from the outside of the separation tube to the inside to improve the output density of the tubular cell.

1 is a schematic diagram of power generation of a general direct carbon fuel cell.

Figure 2 is a block diagram showing a preferred embodiment of a fuel supply device for a direct carbon fuel cell according to the present invention.

3 and 4 are diagrams showing other embodiments according to the method of supplying carbon dioxide in the embodiment of FIG.

5 to 7 correspond to FIGS. 2 to 4 and show other embodiments in which a plurality of tubular cells are configured.

8 is a configuration diagram showing another embodiment in which the configuration of the separation pipe is changed corresponding to FIG. 3.

9 is a configuration diagram showing another embodiment in which the dispersion member is configured in the embodiment of FIG. 2.

Hereinafter, with reference to the accompanying drawings will be described in detail a preferred embodiment of the present invention. The terms used in the present specification and claims are not to be construed as being limited to ordinary or dictionary meanings, but should be interpreted as meanings and concepts corresponding to the technical matters of the present invention.

The embodiments described in the specification and the configuration shown in the drawings are preferred embodiments of the present invention, and do not represent all of the technical idea of the present invention, various equivalents and modifications that can replace them at the time of the present application are There may be.

The present invention discloses a fuel supply apparatus for a direct carbon fuel cell having a structure in which a tubular cell is generated by being immersed in a mixture of an anode medium and a carbon fuel in a liquid state.

Here, the tubular cell has a structure in which an air electrode is formed inside, a fuel electrode is formed outside, and a solid oxide electrolyte is formed between the air electrode and the fuel electrode.

The cathode may be composed of lanthanum-strontium-manganese oxide (LSM), the electrolyte may be composed of yttria stabilized zirconia (YSZ), and the anode may be composed of carbon fuel particles mixed with circulating molten salt.

In addition, molten carbonate may be used as the anode medium, and carbon powder, coal powder, coke, biomass fuel, organic waste, and the like may be used as the carbon fuel.

Referring to FIG. 2, the tubular cell 12 according to the present invention is configured to be contained in at least one molten carbonate, which is the anode medium 14 contained in a bath 10.

In addition, the embodiment according to the present invention comprises a flow passage tube 16 forming a cylindrical flow path in a vertical direction around the tubular cell 12 immersed in the anode medium 14 accommodated in the bath 10.

The flow path tube 16 has a configuration in which an upper portion has a cylindrical shape and a lower portion has a collecting portion 18 having a shape gradually widening downward.

In the embodiment according to the present invention, the separation pipe 30 is configured in the flow path pipe 16. An external flow path is formed between the flow path tube 16 and the separation pipe 30, and the internal flow path is formed while the tubular cell 12 is included in the separation pipe 30.

The separation pipe 30 has a plurality of through holes 32 through which the anode medium 14 can enter and exit, and each through hole 32 is preferably formed to have an inclination rising from the inside to the outside.

The plurality of through holes 32 may be formed in various arrangements and shapes with respect to the wall of the separation pipe 30 according to the intention of the manufacturer, and specific examples thereof will be omitted.

The separation pipe 30 prevents the carbon dioxide moving through the outer flow path from entering the inner flow path by the structure of the through hole 32 having an inclination rising from the inner side to the outer side, and moves through the inner flow path. ) To the outside.

The flow path tube 16 and the separation tube 30 are arranged to be completely immersed in the anode medium 14 to have a configuration in which the anode medium 14 can flow on the upper side and the lower side.

Embodiments according to the present invention include bubbling means for supplying gas to the lower portion of the flow path tube (16). Here, the gas is preferably carbon dioxide (CO ₂ ) generated as a result of the electrochemical reaction of Figure 1, the gas is described as carbon dioxide for the description of the following embodiments.

The bubbling means comprises a supply pipe 20 extending to the lower portion of the flow path tube 16 to supply carbon dioxide as shown in FIG. 2, or from the top along the outer wall of the flow path tube 16 as shown in FIGS. 3 and 4. It may be configured to include a supply pipe 22 extending downward.

When the bubbling means includes a supply pipe 20 extending below the flow path pipe 16 as shown in FIG. 2, the end of the supply pipe 20 is connected to an external flow path between the flow path pipe 16 and the separation pipe 30. It is preferred that the carbon dioxide is supplied directly and formed to rise.

3 and 4, when the bubbling means includes a supply pipe 22 extending from the top to the bottom along the flow pipe 16, an end of the supply pipe 22 is formed inside the bottom of the flow pipe 16. This is preferred. More preferably, the end of the supply pipe 22 is configured to supply carbon dioxide to the external flow path between the flow path pipe 16 and the separation pipe 30 through the collecting portion 18 at the bottom of the flow path pipe 16. Do.

2 and 3, the bubbling means including the

supply pipes

20 and 22 may include a pumping device 24 that independently generates and provides carbon dioxide.

On the contrary, as shown in FIG. 4, the bubbling means may recycle and supply carbon dioxide generated by the electrochemical reaction in the bath 10. To this end, the bubbling means may include a circulation device 26 for recycling a portion of the carbon dioxide generated by the electrochemical reaction in the bath 10 to the outside while recirculating a portion and supplying it through the supply pipe 22.

Referring to FIG. 4, the circulation device 26 may have a configuration in which carbon dioxide collected into the upper portion of the bath 10 is discharged to the outside through the exhaust pipe 28 and a part of the circulation is supplied to the supply pipe 22.

In addition, the

supply pipes

20 and 22 for supplying carbon dioxide in the embodiment according to the present invention of FIGS. 2 to 4 may have a configuration extending while spirally wound to the outside of the flow path tube (16).

As described above, according to the exemplary embodiment configured as shown in FIGS. 2 to 4, carbon dioxide may be supplied to an external flow path between the flow path pipe 16 and the separation pipe 30.

When carbon dioxide supplied from the end of the supply pipe 20 included in the bubbling means is supplied onto the outer flow path between the flow path pipe 16 and the separation pipe 30, the carbon dioxide moves vertically through the outer flow path.

When the carbon dioxide moves vertically along the outer flow path between the flow path tube 16 and the separation pipe 30, the anode medium 14 on the outer flow path may be pushed by the vertically moving carbon dioxide to flow.

At this time, the carbon dioxide rising by the structure of the through hole 32 of the separation pipe 30 is prevented from flowing into the inner flow path.

When carbon dioxide is continuously supplied to the external flow path between the flow path pipe 16 and the separation pipe 30 and the anode medium 14 in the external flow path flows, the external flow path between the flow path pipe 16 and the separation pipe 30 In order to fill the space of the vertically moved carbon dioxide in the lower portion, the anode medium 14 outside the flow path tube 16 is introduced into the outer flow path, and the vertical movement is performed at the top of the outer flow path between the flow path tube 16 and the separation pipe 30. Due to the carbon dioxide, the phenomenon in which the anode medium 14 overflows to the outside occurs.

Thus, the entire anode medium 14 inside the bath 10 can be circulated through the flow path tube 16.

At this time, when the anode medium 14 of the outer flow path between the flow path tube 16 and the separation pipe 30 flows as the carbon dioxide moves, the anode medium 14 on the inner flow path inside the separation pipe 30 is also the outer flow path. It flows upward according to the flow of the anode medium 14 on the bed.

As described above, as the anode medium 14 on the outer flow path and the inner flow path is circulated, the mixing of the carbon fuel and the anode medium 14 may be promoted.

In addition, the carbon fuel and the anode medium 14 promoted by mixing are circulated while contacting the tubular cell 12 through an internal flow path in the separation pipe 30. Therefore, the anode of the tubular cell 12 can be accelerated by the fuel circulated and the anode medium 14.

In addition, a portion of the anode medium 14 flowing upward along the inner flow path inside the separation pipe 30 may move to the outer flow path through the through hole 32.

In addition, since the anode medium 14 on the inner flow path flows, carbon dioxide generated by the reaction may move along the flow of the anode medium 14 without being attached to the outer wall of the tubular cell 12. Therefore, the phenomenon that the reaction is blocked by the carbon dioxide outer wall 12 can be prevented.

The circulation of the anode medium 14 by the carbon dioxide described with reference to FIG. 2 is equally applied to FIGS. 3 and 4, and the effects thereof may be equally expected, and thus redundant description thereof will be omitted.

Meanwhile, in the exemplary embodiment of the present invention, a plurality of tubular cells 12 may be configured in the flow passage 16 as shown in FIGS. 5 to 7. The embodiment according to the invention illustrates that two tubular cells 12 are configured in FIGS. 5 to 7 to illustrate the arrangement of a plurality of tubular cells 12.

FIG. 5 illustrates that two tubular cells 12 are formed in the flow path tube 16 in correspondence with FIG. 2, and FIG. 6 illustrates that two tubular cells 12 in the flow path tube 16 correspond to FIG. 3. FIG. 7 illustrates that two tubular cells 12 are configured in the flow path tube 16 corresponding to FIG. 4.

5 to 7 are different in that a plurality of (two) tubular cells 12 are configured in the flow path tube 16 as compared to FIGS. 2 to 4 and the remaining parts may be configured in the same way. Overlapping configuration and operation description thereof will be omitted.

The number of tubular cells 12 disposed in the flow path tube 16 may be variously modified in consideration of the flow efficiency of the anode medium according to the manufacturer's intention.

5 to 7, the carbon dioxide supplied from the end of the supply pipe (20, 22) included in the bubbling means is supplied to the external flow path between the flow path pipe 16 and the separation pipe 30, the carbon dioxide is moved vertically As a result, the flow of the anode medium 14 on the inner flow path occurs as described with reference to FIGS. 2 to 4.

On the other hand, in the embodiment according to the present invention may be a separation pipe 40 having a configuration as shown in FIG.

In FIG. 8, the separation pipe 40 has a through hole 42 formed therein and a guide 44 corresponding to the through hole 42.

That is, the separation pipe 40 has a configuration including a guide 44 for guiding the flow of the fluid in the inner flow path to the outside.

The guide 44 is configured to be inclined toward the inner bottom while continuing to the upper part of the inlet of the through hole 42.

Therefore, the guide 44 guides the discharge of the fluid (fuel electrode medium 14 or carbon dioxide) flowing downward from the inner passage through the through hole 42 to the outer passage.

The separation pipe 40 of FIG. 8 may be configured in place of the separation pipe 30 of FIGS. 2 to 4, and the effects and effects thereof are the same as those of the embodiments of FIGS. 2 to 4. Omit.

On the other hand, according to the embodiment of the present invention is a dispersion member for dispersing the gas supplied from the supply pipe 20 of the bubbling means to the upper flow path in the flow path tube 16 and the separation pipe 30 as shown in FIG. 50) may be further included.

The dispersion member 50 may be configured as a ring-shaped plate having a plurality of through holes 52 as shown in FIG. According to the manufacturer's intention, the dispersion member 50 may be configured in various shapes, for example, a structure including a porous layer may be illustrated.

Therefore, according to the present invention, the anode medium can be forcibly supplied to the direct carbon fuel cell while ensuring the fluidity of the anode medium and mixing the carbon fuel and the anode medium.

In addition, according to the present invention, a separation pipe may be configured in the flow path pipe, and the flow of the anode medium of the internal flow path in the separation pipe may occur due to the movement of carbon dioxide on the external flow path between the flow path pipe and the separation pipe.

Accordingly, the output density can be improved by reducing the concentration polarization of the anode of the tubular cell.

In addition, according to the present invention, it is possible to prevent the gas of the external flow path from flowing in from the outside of the separation pipe to the inside according to the action of the separation pipe to improve the output density.

Claims

A separator tube forming a cylindrical inner flow path in a vertical direction around the tubular cell contained in the anode medium mixed with carbon fuel and having a through hole through which the anode medium can enter and exit;

A flow path tube forming a cylindrical outer flow path in a vertical direction around the separation pipe; And

And bubbling means for supplying gas to the external flow path between the flow path pipe and the separation pipe.

Direct carbon is characterized in that the anode medium on the outer flow path is primarily flown as the gas supplied to the outer flow path is moved vertically and the anode medium on the inner flow path connected to the outer flow path and the through hole is secondary flow. Fuel supply device of fuel cell.
The method of claim 1,

The flow path tube is a fuel supply device for a direct carbon fuel cell in which the gas is supplied to the lower portion is guided to the external flow path by the collecting portion is formed by the collecting portion of the lower shape is widened.
The method of claim 1,

And a supply pipe for supplying the gas to the bubbling means, and an end portion of the supply pipe is configured to supply the gas to the external flow path between the flow path pipe and the separation pipe.
The method of claim 3, wherein

And the supply pipe of the bubbling means is configured to extend from the top to the bottom along the outer wall of the flow path pipe.
The method of claim 4, wherein

The supply pipe is a fuel supply device for a direct carbon fuel cell is formed spirally along the outer wall of the flow pipe.
The method of claim 1,

And a dispersing member configured to disperse the gas supplied from the bubbling means to the upper flow path between the flow path pipe and the separation pipe to supply the gas to the upper flow path.
The method of claim 6,

The dispersion member is a fuel supply device for a direct carbon fuel cell composed of a ring-shaped plate having a plurality of through holes.
The method of claim 6,

The dispersion member is a fuel supply device for a direct carbon fuel cell comprising a porous layer.
The method of claim 1,

The bubbling means is a fuel supply device for a direct carbon fuel cell to independently generate and provide the gas.
The method of claim 1,

The bubbling means is a fuel supply device of a direct carbon fuel cell for supplying by recycling the gas generated by the electrochemical reaction of the carbon fuel and discharged to the outside of the anode medium.
The method of claim 1,

The through hole of the separation pipe is a fuel supply device of a direct carbon fuel cell is formed to have a slope rising to the outside.
The method of claim 1,

The separator pipe is a fuel supply device for a direct carbon fuel cell is formed in the inner wall of the guide to guide the flow of the fluid to the outside in contact with the through hole.
The method of claim 1,

The gas is a fuel supply device for a direct carbon fuel cell containing carbon dioxide.
The method of claim 1,

The anode medium is a fuel supply device for a direct carbon fuel cell containing molten carbonate.
The method of claim 1,

The separator pipe is a fuel supply device for a direct carbon fuel cell to form the inner passage around a plurality of tubular cells.
At least one tubular cell having a structure in which a cathode is formed inside, a fuel electrode is formed at an outer surface, and an electrolyte is formed of a solid oxide between the cathode and the anode; And

And a fuel supply device according to any one of claims 1 to 15, for supplying a fuel cell medium forced to the tubular cell.